Designed to Degrade: Tailoring Polyesters for Circularity.

A powerful toolbox is needed to turn the linear plastic economy into circular. Development of materials designed for mechanical recycling, chemical recycling, and/or biodegradation in targeted end-of-life environment are all necessary puzzle pieces in this process. Polyesters, with reversible ester bonds, are already forerunners in plastic circularity: poly(ethylene terephthalate) (PET) is the most recycled plastic material suitable for mechanical and chemical recycling, while common aliphatic polyesters are biodegradable under favorable conditions, such as industrial compost. However, this circular design needs to be further tailored for different end-of-life options to enable chemical recycling under greener conditions and/or rapid enough biodegradation even under less favorable environmental conditions. Here, we discuss molecular design of the polyester chain targeting enhancement of circularity by incorporation of more easily hydrolyzable ester bonds, additional dynamic bonds, or degradation catalyzing functional groups as part of the polyester chain. The utilization of polyester circularity to design replacement materials for current volume plastics is also reviewed as well as embedment of green catalysts, such as enzymes in biodegradable polyester matrices to facilitate the degradation process.

Peptide direct growth on poly(acrylic acid)/poly(vinyl alcohol) electrospun fibers coated with branched poly(ethylenimine): A solid-phase approach for scaffolds biofunctionalization.

Due to their resemblance to the fibrillar structure of the extracellular matrix, electrospun nanofibrous meshes are currently used as porous and mechanically stable scaffolds for cell culture. In this study, we propose an innovative methodology for growing peptide sequences directly onto the surface of electrospun nanofibers. To achieve this, electrospun fibers were produced from a poly(acrylic acid)/poly(vinyl alcohol) blend that was thermally crosslinked and subjected to a covalent coating of branched poly(ethylenimine). The exposed amino functionalities on the fiber surface were then used for the direct solid-phase synthesis of the RGD peptide sequence. In contrast to established strategies, mainly involving the grafting of pre-synthesized peptides onto the polymer chains before electrospinning or onto the nanofibers surface, this method allows for the concurrent synthesis and anchoring of peptides to the substrate, with potential applications in combinatorial chemistry. The incorporation of this integrin-binding motive significantly enhanced the nanofibers' ability to capture human cervical carcinoma (HeLa) cells, selected as a proof of concept to assess the functionalities of the developed material.

Simple Non-Equilibrium Atmospheric Plasma Post-Treatment Strategy for Surface Coating of Digital Light Processed 3D-Printed Vanillin-Based Schiff-Base Thermosets.

A simple non-equilibrium atmospheric plasma post-treatment strategy was developed for the surface coating of three-dimensional (3D) structures produced by digital light processing 3D printing. The influence of non-equilibrium atmospheric plasma on the chemical and physical properties of vanillin-derived Schiff-base thermosets and the dip-coating process was investigated and compared to the influence of traditional post-treatment with UV-light. As a comparison, thermosets without post-treatment were also subjected to the coating procedure. The results document that UV post-treatment can induce the completion of the curing of the printed thermosets if complete curing is not reached during printing. Conversely, the plasma post-treatment does not contribute to the curing of the thermoset but causes some opening of the imine bonds and the regeneration of aldehyde functions. As a consequence, no great differences are observed between the not post-treated and plasma post-treated samples in terms of mechanical, thermal, and solvent-resistant properties. In contrast to the UV post-treatment, the plasma post-treatment of the thermosets induces a noticeable increase of the thermoset hydrophilicity ascribed to the reformation of amines on the thermoset surface. The successful coating process and the greatest uniformity of the lignosulfonate coating on the surface of plasma post-treated samples are considered to be due to the presence of these amines and aldehydes. The investigation of the UV shielding properties and antioxidant activities documents the increase of both properties with the increasing amount and uniformity of the formed coating. Interestingly, evident antioxidant properties are also shown by the noncoated thermosets, which are deduced to their chemical structures.

Digital Light Processing 3D Printing of Isosorbide- and Vanillin-Based Ester and Ester-Imine Thermosets: Structure-Property Recyclability Relationships.

Four isosorbide-based photocurable resins were designed to reveal correlations between the composition and chemical structure, digital light processing (DLP) three-dimensional (3D) printability, thermoset properties, and recyclability. Especially, the role of functional groups, i.e., the concentration of ester groups vs the combination of ester and imine functionalities, in the recyclability of the resins was investigated. The resins consisted of methacrylated isosorbide alone or in combination with methacrylated vanillin or a flexible methacrylated vanillin Schiff-base. The composition of the resins significantly affected their 3D printability as well as the physical and chemical properties of the resulting thermosets. The results indicated the potential of methacrylated isosorbide to confer rigidity to thermosets with some negative effects on the printing quality and solvent-resistance properties. An increase in the methacrylated vanillin concentration in the resin enabled us to overcome these drawbacks, leading, however, to thermosets with lower thermal stability. The replacement of methacrylated vanillin with the methacrylated Schiff-base resin decreased the rigidity of the networks, ensuring, on the other hand, improved solvent-resistance properties. The results highlighted an almost complete preservation of the elastic modulus after the reprocessing or chemical recycling of the ester-imine thermosets, thanks to the presence of two distinct dynamic covalent bonds in the network; however, the concentration of the ester functions in the ester thermosets played a significant role in the success of the chemical recycling procedure.

Controlled Release of H2S from Biomimetic Silk Fibroin-PLGA Multilayer Electrospun Scaffolds.

The possibility of incorporating H2S slow-release donors inside biomimetic scaffolds can pave the way to new approaches in the field of tissue regeneration and anti-inflammatory treatment. In the present work, GYY4137, an easy-to-handle commercially available Lawesson's reagent derivative, has been successfully incorporated inside biomimetic silk fibroin-based electrospun scaffolds. Due to the instability of GYY4137 in the solvent needed to prepare silk fibroin solutions (formic acid), the electrospinning of the donor together with the silk fibroin turned out to be impossible. Therefore, a multilayer structure was realized, consisting of a PLGA mat containing GYY4137 sandwiched between two silk fibroin nanofibrous layers. Before their use in the multilayer scaffold, the silk fibroin mats were treated in ethanol to induce crystalline phase formation, which conferred water-resistance and biomimetic properties. The morphological, thermal, and chemical properties of the obtained scaffolds were thoroughly characterized by SEM, TGA, DSC, FTIR, and WAXD. Multilayer devices showing two different concentrations of the H2S donor, i.e., 2 and 5% w/w with respect to the weight of PLGA, were analyzed to study their H2S release and biological properties, and the results were compared with those of the sample not containing GYY4137. The H2S release analysis was carried out according to an "ad-hoc" designed procedure based on a validated high-performance liquid chromatography method. The proposed analytical approach demonstrated the slow-release kinetics of H2S from the multilayer scaffolds and its tunability by acting on the donor's concentration inside the PLGA nanofibers. Finally, the devices were tested in biological assays using bone marrow-derived mesenchymal stromal cells showing the capacity to support cell spreading throughout the scaffold and prevent cytotoxicity effects in serum starvation conditions. The resulting devices can be exploited for applications in the tissue engineering field since they combine the advantages of controlled H2S release kinetics and the biomimetic properties of silk fibroin nanofibers.

A new strategy to prevent biofilm and clot formation in medical devices: The use of atmospheric non-thermal plasma assisted deposition of silver-based nanostructured coatings.

In industrialized countries, health care associated infections, the fourth leading cause of disease, are a major health issue. At least half of all cases of nosocomial infections are associated with medical devices. Antibacterial coatings arise as an important approach to restrict the nosocomial infection rate without side effects and the development of antibiotic resistance. Beside nosocomial infections, clot formation affects cardiovascular medical devices and central venous catheters implants. In order to reduce and prevent such infection, we develop a plasma-assisted process for the deposition of nanostructured functional coatings on flat substrates and mini catheters. Silver nanoparticles (Ag NPs) are synthesized exploiting in-flight plasma-droplet reactions and are embedded in an organic coating deposited through hexamethyldisiloxane (HMDSO) plasma assisted polymerization. Coating stability upon liquid immersion and ethylene oxide (EtO) sterilization is assessed through chemical and morphological analysis carried out by means of Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). In the perspective of future clinical application, an in vitro analysis of anti-biofilm effect has been done. Moreover, we employed a murine model of catheter-associated infection which further highlighted the performance of Ag nanostructured films in counteract biofilm formation. The anti-clot performances coupled by haemo- and cytocompatibility assays have also been performed.

Electrospun fibers coated with nanostructured biomimetic hydroxyapatite: A new platform for regeneration at the bone interfaces.

Reconstruction of gradient organic/inorganic tissues is a challenging task in orthopaedics. Indeed, to mimic tissue characteristics and stimulate bone regeneration at the interface, it is necessary to reproduce both the mineral and organic components of the tissue ECM, as well as the micro/nano-fibrous morphology. To address this goal, we propose here novel biomimetic patches obtained by the combination of electrospinning and nanostructured bone apatite. In particular, we deposited apatite on the electrospun fibers by Ionized Jet Deposition, a plasma-assisted technique that allows conformal deposition and the preservation in the coating of the target's stoichiometry. The damage to the substrate and fibrous morphology is a polymer-dependent aspect, that can be avoided by properly selecting the substrate composition and deposition parameters. In fact, all the tested polymers (poly(l-lactide), poly(D,l-lactide-co-glycolide, poly(ε-caprolactone), collagen) were effectively coated, and the morphological and thermal characterization revealed that poly(ε-caprolactone) suffered the least damage. The coating of collagen fibers, on the other hand, destroyed the fiber morphology and it could only be performed when collagen is blended with a more resistant synthetic polymer in the nanofibers. Due to the biomimetic composition and multiscale morphology from micro to nano, the poly(ε-caprolactone)-collagen biomimetic patches coated with bone apatite supported MSCs adhesion, patch colonization and early differentiation, while allowing optimal viability. The biomimetic coating allowed better scaffold colonization, promoting cell spreading on the fibers.

A Modular Composite Device of Poly(Ethylene Oxide)/Poly(Butylene Terephthalate) (PEOT/PBT) Nanofibers and Gelatin as a Dual Drug Delivery System for Local Therapy of Soft Tissue Tumors.

In the clinical management of solid tumors, the possibility to successfully couple the regeneration of injured tissues with the elimination of residual tumor cells left after surgery could open doors to new therapeutic strategies. In this work, we present a composite hydrogel-electrospun nanofiber scaffold, showing a modular architecture for the delivery of two pharmaceutics with distinct release profiles, that is potentially suitable for local therapy and post-surgical treatment of solid soft tumors. The composite was obtained by coupling gelatin hydrogels to poly(ethylene oxide)/poly(butylene terephthalate) block copolymer nanofibers. Results of the scaffolds' characterization, together with the analysis of gelatin and drug release kinetics, displayed the possibility to modulate the device architecture to control the release kinetics of the drugs, also providing evidence of their activity. In vitro analyses were also performed using a human epithelioid sarcoma cell line. Furthermore, publicly available expression datasets were interrogated. Confocal imaging showcased the nontoxicity of these devices in vitro. ELISA assays confirmed a modulation of IL-10 inflammation-related cytokine supporting the role of this device in tissue repair. In silico analysis confirmed the role of IL-10 in solid tumors including 262 patients affected by sarcoma as a negative prognostic marker for overall survival. In conclusion, the developed modular composite device may provide a key-enabling technology for the treatment of soft tissue sarcoma.

Designed from Biobased Materials for Recycling: Imine-Based Covalent Adaptable Networks.

Turning thermosets into fully sustainable materials requires utilization of biobased raw materials and design for easy recyclability. Here, dynamic covalent chemistry for fabrication of covalent adaptable networks (CANs) could be an enabling tool. CAN thermosets ideally combine the positive material properties of thermosets with thermal recyclability of linear thermoplastics. Among the dynamic covalent bonds, imine bond, also called Schiff base, can participate in both dissociative and associative pathways. This induces potential for chemical recyclability, thermal reprocessability and self-healing. This review presents an overview of the current research front of biobased thermosets fabricated by Schiff base chemistry. The discussed materials are categorized on the basis of the employed biobased components. The chemical approaches for the synthesis and curing of the resins, as well as the resulting properties and recyclability of the obtained thermosets are described and discussed. Finally, challenges and future perspectives are briefly summarized.

Nanocomposite electrospun fibers of poly(ε-caprolactone)/bioactive glass with shape memory properties.

Electrospun fibers of shape memory triethoxysilane-terminated poly(epsilon-caprolactone) (PCL-TES) loaded with bioactive glasses (BG) are here presented. Unloaded PCL-TES, as well as PCL/BG nanocomposite fibers, are also considered for comparison. It is proposed that hydrolysis and condensation reactions take place between triethoxysilane groups of the polymer and the silanol groups at the BG particle surface, thus generating additional crosslinking points with respect to those present in the PCL-TES system. The as-spun PCL-TES/BG fibers display excellent shape memory properties, in terms of shape fixity and shape recovery ratios, without the need of a thermal crosslinking treatment. BG particles confer in vitro bioactivity to PCL-based nanocomposite fibers and favor the precipitation of hydroxycarbonate apatite on the fiber surface. Preliminary cytocompatibility tests demonstrate that the addition of BG particles to PCL-based polymer does not inhibit ST-2 cell viability. This novel approach of using bioactive glasses not only for their biological properties, but also for the enhancement of shape memory properties of PCL-based polymers, widens the versatility and suitability of the obtained composite fibers for a huge portfolio of biomedical applications.

Thermoactive Smart Electrospun Nanofibers.

The recent burst of research on smart materials is a clear evidence of the growing interest of the scientific community, industry, and society in the field. The exploitation of the great potential of stimuli-responsive materials for sensing, actuation, logic, and control applications is favored and supported by new manufacturing technologies, such as electrospinning, that allows to endow smart materials with micro- and nanostructuration, thus opening up additional and unprecedented prospects. In this wide and lively scenario, this article systematically reviews the current advances in the development of thermoactive electrospun fibers and textiles, sorting them, according to their response to the thermal stimulus. Hence, several platforms including thermoresponsive systems, shape memory polymers, thermo-optically responsive systems, phase change materials, thermoelectric materials, and pyroelectric materials, are described and critically discussed. The difference in active species and outputs of the aforementioned categories is highlighted, evidencing the transversal nature of temperature stimulus. Moreover, the potential of novel thermoactive materials are pointed out, revealing how their development could take to utmost interesting achievements.

Nanotechnology-Assisted RNA Delivery: From Nucleic Acid Therapeutics to COVID-19 Vaccines.

In recent years, the main quest of science has been the pioneering of the groundbreaking biomedical strategies needed for achieving a personalized medicine. Ribonucleic acids (RNAs) are outstanding bioactive macromolecules identified as pivotal actors in regulating a wide range of biochemical pathways. The ability to intimately control the cell fate and tissue activities makes RNA-based drugs the most fascinating family of bioactive agents. However, achieving a widespread application of RNA therapeutics in humans is still a challenging feat, due to both the instability of naked RNA and the presence of biological barriers aimed at hindering the entrance of RNA into cells. Recently, material scientists' enormous efforts have led to the development of various classes of nanostructured carriers customized to overcome these limitations. This work systematically reviews the current advances in developing the next generation of drugs based on nanotechnology-assisted RNA delivery. The features of the most used RNA molecules are presented, together with the development strategies and properties of nanostructured vehicles. Also provided is an in-depth overview of various therapeutic applications of the presented systems, including coronavirus disease vaccines and the newest trends in the field. Lastly, emerging challenges and future perspectives for nanotechnology-mediated RNA therapies are discussed.

The diterpene Manool extracted from Salvia tingitana lowers free radical production in retinal rod outer segments by inhibiting the extramitochondrial F1 Fo ATP synthase.

Uncontrolled oxidative stress production, especially in the outer retina is one of the causes of retinal degenerations. Mitochondria are considered the principal source of oxidative stress. However, a Reactive Oxygen Intermediates (ROI) production in the retinal photoreceptor layer seems to depend also on the expression of an extramitochondrial oxidative phosphorylation (OxPhos) machinery in the rod outer segments (OS). In fact, OS conduct aerobic metabolism, producing ATP through oxygen consumption, although it is devoid of mitochondria. As diterpenes display an antioxidant effect, we have evaluated the effect Manool, extracted from Salvia tingitana, on the extramitochondrial OxPhos and the ROI production in the retinal rod OS. Results confirm that the OxPhos machinery is ectopically expressed in the OS and that F1 Fo -ATP synthase is a target of Manool, which inhibited the OS ATP synthesis, binding the F1 moiety with high affinity, as analysed by molecular docking. Moreover, the overall slowdown of OxPhos metabolism reduced the ROI production elicited in the OS by light exposure, in vitro. In conclusion, data are consistent with the antioxidant properties of Salvia spp., suggesting its ability to lower oxidative stress production, a primary risk factor for degenerative retinal diseases. SIGNIFICANCE OF THE STUDY: Here we show that Manool, a diterpene extracted from Salvia tingitana has the potential to lower the free radical production by light-exposed rod outer segments in vitro, by specifically targeting the rod OS F1 Fo -ATP synthase belonging to the extramitochondrial OxPhos expressed on the disk membrane. The chosen experimental model allowed to show that the rod OS is a primary producer of oxidative stress linked to the pathogenesis of degenerative retinal diseases. Data are also consistent with the antioxidant and anti-inflammatory action of Salvia spp., suggesting a beneficial effect also in vivo.

Elastomeric Electrospun Scaffolds of a Biodegradable Aliphatic Copolyester Containing PEG-Like Sequences for Dynamic Culture of Human Endothelial Cells.

In the field of artificial prostheses for damaged vessel replacement, polymeric scaffolds showing the right combination of mechanical performance, biocompatibility, and biodegradability are still demanded. In the present work, poly(butylene-co-triethylene trans-1,4-cyclohexanedicarboxylate), a biodegradable random aliphatic copolyester, has been synthesized and electrospun in form of aligned and random fibers properly designed for vascular applications. The obtained materials were analyzed through tensile and dynamic-mechanical tests, the latter performed under conditions simulating the mechanical contraction of vascular tissue. Furthermore, the in vitro biological characterization, in terms of hemocompatibility and cytocompatibility in static and dynamic conditions, was also carried out. The mechanical properties of the investigated scaffolds fit within the range of physiological properties for medium- and small-caliber blood vessels, and the aligned scaffolds displayed a strain-stiffening behavior typical of the blood vessels. Furthermore, all the produced scaffolds showed constant storage and loss moduli in the investigated timeframe (24 h), demonstrating the stability of the scaffolds under the applied conditions of mechanical deformation. The biological characterization highlighted that the mats showed high hemocompatibility and low probability of thrombus formation; finally, the cytocompatibility tests demonstrated that cyclic stretch of electrospun fibers increased endothelial cell activity and proliferation, in particular on aligned scaffolds.

Men, Women, and Economic Changes: Social Representations of the Economic Crisis / Hombres, mujeres y cambios económicos: representaciones sociales de la crisis económica

Resumen La crisis económica actual ha sido un fenómeno nuevo e inesperado; es parte del sistema capitalista, bancario y económico que ha sido conocido hasta el año 2008. La crisis ha llevado a los bancos, los Estados, las instituciones internacionales, así como a las personas del común, a ver profundos cambios en sus representaciones sobre la economía. En este escenario, se plantea la pregunta: ¿cómo los hombres y las mujeres de estratos sociales diferentes afrontan el fenómeno complejo y desconocido de la crisis económica? ¿El género y el estatus social justifican diferentes significados atribuidos a la crisis, sus causas y consecuencias? En el presente artículo se elige la teoría de las representaciones sociales para estudiar el papel del género y el nivel educativo en la producción de las representaciones de la crisis. Se presentan resultados de encuestas realizadas en el sur de Italia (N = 120), los cuales revelan que tanto el género como el nivel educativo de las personas marcan diferencias en la forma de definir y afrontar la crisis. Por un lado, los participantes de alto nivel definen la crisis en términos más abstractos que los participantes de bajo nivel. Por otra parte, los hombres de alto nivel mantienen un estado de coping más proactivo con la crisis que los otros participantes, especialmente mujeres. La discusión se enfoca en el papel de la teoría de la representación social entendiendo la relación entre género, estatus y comportamiento económico, aportando ideas sobre cómo la igualdad de género puede ser mejorada.

Abstract The current economic crisis has been a new and unexpected phenomenon; it is part of the capitalist banking and economic system that has been known until 2008. The crisis has led to banks, states, international institutions, as well as common people, changing profoundly their representations about the economy. In this scenario, some questions arise: how do men and women of different social status face the complex and unknown phenomenon of the economic crisis? Do gender and social status justify the different meanings attributed to the crisis, to its causes and its consequences? When confronted with an external threat like the economic crisis, people draw on social representations to provide meaning to that unfamiliar situation. Through media and interpersonal communication, social groups produce naive theories that improve familiarity with an unexpected and distressing phenomenon. In order to analyze these lay theories elaborated though daily economic thinking and acting, this research has been conducted using Social Representation Theory and its methodological approaches. This theory, in fact, contributes to our understanding of the societal process of sense making when an unexperienced external shock affects society. It offers a way to understand economic phenomena's impact on social groups. Social representations (SRs) serve the purpose of making the unfamiliar become familiar, and the unusual become usual, as well as to provide orientation in times of change. In this sense, in this article, social representations theory is used to examine the role of gender and educational status in the production of representations of the crisis. Presented findings came from a survey carried out in Southern Italy (N = 120) revealing status and gender differences in the ways people define the crisis and cope with it. Participants were asked to order the first most important five statements and the first least important statements, among a list of 15 (according to the rule of a multiple of 3) to code every item with a score of 1 (less characteristic), 3 (more characteristic), or 2 (not chosen). Every Questionnaire of Characterization was created starting from social descriptions and explanations of the crisis, identified in a previous study. They covered every sub-dimension of the content (complementary to the structure) of the social representation of the crisis, such as: cognitive-evaluative aspects about the representation's structure (central and peripheral elements); descriptive-defining aspects of the representation; informative sources and interaction networks; level of involvement/implication with the object; relationship between representation and social practices; perceptions, attributions and categorizations (causes, responsibilities, duration/evolution, solutions, positive implications, the EU's role). In this paper, we will only consider the answers related to the following dimensions: crisis definitions, strategies to tackle the crisis and social practices related to the crisis. The analysis of the data was carried out primarily using Multiple Correspondence Analysis (MCA). In this analysis, in order to uncover the objectification and anchoring processes, we considered the interaction of status and gender as an illustrative variable. These findings were further substantiated with the use of Discriminant analysis. The social anchoring of social representations of the economic crisis is influenced by gender and social status. Nevertheless, the difference in status modifies the stereotypical dimensions, also coherently with predictions derived from gender role theory about the reduction of the impact of gender stereotypes when men and women occupy similar social positions. On the one hand, high-status participants defined the crisis in more abstract terms than low-status participants. On the other hand, high-status men hold a more proactive style of coping with the crisis than other participants, especially women. The discussion focuses on the role of social representations theory in understanding the relationships between gender, status and economic behavior, providing insights into how gender equality might be improved.

Electrospinning of Fish Gelatin Solution Containing Citric Acid: An Environmentally Friendly Approach to Prepare Crosslinked Gelatin Fibers.

The majority of the crosslinking approaches employed to confer water resistance properties to electrospun gelatin mats are based on the use of potential cytotoxic agents, turning out to be not suitable for biomedical applications. Environmentally friendly chemical strategies based on the use of non-toxic agents are, therefore, strongly demanded. In the present work, the possibility to produce crosslinked electrospun fish gelatin mats by electrospinning an aqueous solution, containing citric acid as a crosslinking agent, is reported. The effect of pH on solution rheological properties, as well as on the electrospun mat morphology, chemistry, and crosslinking degree, is assessed. The increase of solution pH from 1.8 to 3.7 allows for obtaining fibers that maintain the fibrous morphology also in the mat. Subsequent thermal treatment of the electrospun mat (80 °C for 30 min) turns out to increase the crosslinking degree and morphological stability of the mat.

Non-equilibrium atmospheric pressure plasma as innovative method to crosslink and enhance mucoadhesion of econazole-loaded gelatin films for buccal drug delivery.

In this paper we developed an innovative, effective and rapid one-step approach to crosslink mucoadhesive gelatin films for buccal drug delivery. The method, which involves the application of non-equilibrium pressure plasma for 3 or 5 minutes/side, was compared with a classical approach based on the use of a chemical crosslinking agent, namely genipin. Econazole nitrate (ECN), an imidazole antifungal agent used for the treatment of skin infections and mucosal candidiasis, was selected as model drug. X-Ray Diffraction characterization performed on the drug-containing gelatin films revealed that ECN undergoes to a topotactic transformation into Econazole (EC) immediately after mixing with gelatin suggesting the occurrence of an acid-base reaction between drug and gelatin during film processing. Plasma treatment, as well as genipin crosslinking, did not provoke any further variation of EC structure. However, plasma exposure significantly improved films adhesiveness and allowed to reach mucoadhesive strength values more than double with respect to those obtained with genipin, ascribable to the presence of polar and hydrophilic groups on the plasma treated film's surface. A residence time of at least 48 h was obtained by properly selecting the plasma exposure times. These results, together with the in-vitro data showing retention of antifungal efficacy against a strain of Candida albicans, demonstrated that plasma treatment was a valid and rapid alternative, easy to scale-up, to chemical crosslinking methods for the production of highly mucoadhesive gelatin-based films.

Atmospheric Pressure Non-Equilibrium Plasma as a Green Tool to Crosslink Gelatin Nanofibers.

Electrospun gelatin nanofibers attract great interest as a natural biomaterial for cartilage and tendon repair despite their high solubility in aqueous solution, which makes them also difficult to crosslink by means of chemical agents. In this work, we explore the efficiency of non-equilibrium atmospheric pressure plasma in stabilizing gelatin nanofibers. We demonstrate that plasma represents an innovative, easy and environmentally friendly approach to successfully crosslink gelatin electrospun mats directly in the solid state. Plasma treated gelatin mats display increased structural stability and excellent retention of fibrous morphology after immersion in aqueous solution. This method can be successfully applied to induce crosslinking both in pure gelatin and genipin-containing gelatin electrospun nanofibers, the latter requiring an even shorter plasma exposure time. A complete characterization of the crosslinked nanofibres, including mechanical properties, morphological observations, stability in physiological solution and structural modifications, has been carried out in order to get insights on the occurring reactions triggered by plasma.

Poly-l-Lactic Acid Nanofiber-Polyamidoamine Hydrogel Composites: Preparation, Properties, and Preliminary Evaluation as Scaffolds for Human Pluripotent Stem Cell Culturing.

Electrospun poly-l-lactic acid (PLLA) nanofiber mats carrying surface amine groups, previously introduced by nitrogen atmospheric pressure nonequilibrium plasma, are embedded into aqueous solutions of oligomeric acrylamide-end capped AGMA1, a biocompatible polyamidoamine with arg-gly-asp (RGD)-reminiscent repeating units. The resultant mixture is finally cured giving PLLA-AGMA1 hydrogel composites that absorb large amounts of water and, in the swollen state, are translucent, soft, and pliable, yet as strong as the parent PLLA mat. They do not split apart from each other when swollen in water and remain highly flexible and resistant, since the hydrogel portion is covalently grafted onto the PLLA nanofibers via the addition reaction of the surface amine groups to a part of the terminal acrylic double bonds of AGMA1 oligomers. Preliminary tested as scaffolds, the composites prove capable of maintaining short-term undifferentiated cultures of human pluripotent stem cells in feeder-free conditions.

Investigation of the antimicrobial activity at safe levels for eukaryotic cells of a low power atmospheric pressure inductively coupled plasma source.

Low power atmospheric pressure inductively coupled thermal plasma sources integrated with a quenching device (cold ICP) for the efficient production of biologically active agents have been recently developed for potential biomedical applications. In the present work, in vitro experiments aimed at assessing the decontamination potential of a cold ICP source were carried out on bacteria typically associated with chronic wounds and designed to represent a realistic wound environment; further in vitro experiments were performed to investigate the effects of plasma-irradiated physiological saline solution on eukaryotic cells viability. A thorough characterization of the plasma source and process, for what concerns ultraviolet (UV) radiation and nitric oxide production as well as the variation of pH and the generation of nitrates and nitrites in the treated liquid media, was carried out to garner fundamental insights that could help the interpretation of biological experiments. Direct plasma treatment of bacterial cells, performed at safe level of UV radiation, induces a relevant decontamination, both on agar plate and in physiological saline solution, after just 2 min of treatment. Furthermore, the indirect treatment of eukaryotic cells, carried out by covering them with physiological saline solution irradiated by plasma, in the same conditions selected for the direct treatment of bacterial cells does not show any noticeable adverse effect to their viability. Some considerations regarding the role of the UV radiation on the decontamination potential of bacterial cells and the viability of the eukaryotic ones will be presented. Moreover, the effects of pH variation, nitrate and nitrite concentrations of the plasma-irradiated physiological saline solution on the decontamination of bacterial suspension and on the viability of eukaryotic cells subjected to the indirect treatment will be discussed. The obtained results will be used to optimize the design of the ICP source for an effective production of reactive species, while keeping effluent temperature and UV radiation at values compatible with biomedical treatments.